Titanium pigment production



United States Patent @ffice 35M335 Patented May 5, 1970 US. Cl. 106300 8 Claims meow.-.

ABSTRACT OF THE DISCLOSURE A fade-resistant, opacifying co-oxidized TiO -Al O pigment, with 0.1 to A1 0 content based on the TiO content, having a porous SiO coating, of l to 25% SiO based on the TiO obtained upon calcination at 300 C. to 1000 C. of the SiO coated TiO -Al O pigment material.

This invention relates to titanium dioxide pigments and more particularly to the production of improved discoloration resistant aluminum oxide-containing TiO pigments resulting from the -cooxidation of titanium tetrachoride and aluminum chloride useful in the production of pigmented resinous materials, especially paper laminates.

Al O -containing TiO White pigments are well known and adaptable for use in various pigmenting applications, including coating compositions, such as paints, enamels and lacquers, and as delusterants for artificial fibers such as rayon, nylon, etc. Useful procedures for their preparation are disclosed in Us. Pat. 2,559,638, wherein TiCl and controlled, small amounts of AlCl are co-oxidized with air or oxygen at a relatively high temperature ranging from about 800 to 1350 C. The resulting product comprises a soft-textured pigment in uniform, small particle size, with an average particle size radius in the range of from 0.05 to 0.5 micron and preferably from .1 to .25 microns. A1 0 present in the pigment as an essential ingredient ranges from about .1 to 10%, and preferably ranges from 0.5 to 3.5% by weight, based on the TiO In my copending US. application Ser. No. 387,790, filed Aug. 5, 1964, now US. Pat. 3,410,708, useful procedures are disclosed for enhancing the gloss, chalk resistance and weatherability characteristics of this pigment by subjecting the product emitted from the oxidation reactor of the flame process to wet treatment with sufficient porous silica (SiO to completely coat the pigment particles and in amounts preferably ranging from about 25% by weight of the finished pigment. Thereafter, the treated pigment is recovered from the slurry by filtration, dried at about 150 C. and ground to desired fineness texture. It is then incorporated as a pigmenting ingredient in paints, enamels and lacquers.

It has now been found that if the SiO treated TiO Al O product of my prior application is after-treated by calcination at a relatively high temperature rather than dried at a relatively low temperature, quite unexpectedly the resulting porous SiO coated product is outstandingly useful for incorporation in resinous materials, especially paper laminates, as an opacifying pigment and provides a pigment-resin composition which when exposed to sunlight will not dis-color or fade.

It is among the objects of this invention therefore to provide a novel form of TiO -Al O -SiO pigment adapted for use in forming opacified resinous compositions which are photochemically stable to ultraviolet light, and particularly opacified melamine formaldehyde, urea formaldehyde, phenol formaldehyde type resins, especially paper laminates obtained by impregnating the resinous material with my improved opaque pigmenting substance. Such laminates comprise fiat sheets used for counter tops, shelving and panelling, etc.

In accordance with this invention, the following process steps are undertaken:

(l) The TlOz'AlzOg product from the TiCl -AlCl oxidation is directly quenched upon discharge from the reactor by mixing the product with water to form an aqueous slurry containing from 20-40% TiO -Al O by weight.

(2) The resulting slurry is then heated to temperatures within a range of from 40 to 70 C.

(3) An alkali metal silicate, such as sodium silicate (N212 SiO is rapidly mixed with said surry and in quantities equivalent to from 125% SiO based on the weight of the dry TiO pigment being treated.

(4) The sodium silicate-treated slurry is then held at said 4070 C. temperatures with accompanying agitation for a period of about 30 minutes in order to effect desired aging or conditioning of the slurry.

(5) Thereafter the pH of the heated and aged slurry is adjusted through sufiicient acid addition to a pH in the range of from 6-6.5.

(6) The neutralized slurry thus obtained is then held for an additional period of about 30 minutes with agitation at said 4070 C., after which is conventionally filtered and the treated pigment is dried and ground to break up undesired agglomerates.

As noted, these procedures entail a wet process for producing a porous silicate coating on TiO -Al O pigments conveniently brought about by forming an aqueous pigment slurry containing 20-40% TiO -Al O pigment, by weight, directly discharging into and quenching the pigment in water in a suitable corrosion resistant vessel such as a wooden, glass or plastic-lined tank, as it emits from the oxidation reactor or the cooling or calcining equipment. The use of more dilute or concentrated slurries is avoided because of their failure to produce the desired final form of SiO coating.

Slurries made up from calciner discharge are usually neutral, whereas those perpared directly from reactor discharge are usually mildly acidic and in a pH range of from 26. A neutral form of slurry can be readily adjusted to the desired 2-6 pH range by adding thereto a sufficient concentration of mineral acid prior to alkali silicate and SiO treatment. The choice of mineral acid utilized is relatively important in the process since the type and nature of the SiO coating ultimately obtained will be found to depend upon the acid used. Thus, chalkfade resistance in exterior paint films will be found to increase in the sequence of the following acids used: H PO H SO HCI HNO with the latter two acids being about 3 times better than and hence preferred over use of the first two acids. For certain applications where gloss characteristics are more critical and important than chalking properties, recourse to sulfuric acid or hydrochloric acid is preferred This difference in the physical nature of the SiO coating obtained with the use of solutions acidified with the various, different mineral acids mentioned is not presently clearly understood.

Following acidification, should this be necessary to provide a desired 26 pH range, heating of the slurry to a temperature in the range of from 40 C. to 70 C. and preferably to about 60 C. 15 C. is undertaken. Since temperatures in excess of 70 C. tend to form undesired denser silica coatings on the pigment particles, such excessive temperatures are avoided, as are temperatures be ow 40 C. which induce an undesired slow reaction rate.

The hot 4070 C. slurry is then mixed with a solution of an alkali metal silicate, preferably sodium silicate (Na sios), containing in the range of from -400 g ns/liter of SiC Such m' 'ig is quickly effected and with accompanying mild agitation of the slurry by means of conventional stirring equipment. Addition of the silicate solution is continued until the amount of SiO present in the mixture is equivalent to from 1 2502; of the weight of the TiC' -Al O pigment, and preferably ranges in amount to from 2-5% SiO by weight. On completion of silicate addition, the pi i. of the silicate 2 slurry should be at least 9 and may range up to pit 11, depending upon the amount of sodium silicate UllllL Cl. Agitation is continued for about 30 minutes after silicate introduction, and the slurry is then neutralized to a 6*65 p by incorporating therein a sufficient quantity of a suitable mineral acid to result in pr pitation and coalescense of SiO as a coating completely covering the pigment. The choice of acid employed wi as above noted, bear directly not only on the quality of the coating formed but on the ultimate pigment characteristics of the product obtained.

Upon desired slurry aging and SiO precipitation, a further conditioning treatment is undertaken. This is preferably carried out at a pH of 6 6.5 and for an additional 3060 minutes while maintaining the slurry at 4070 if desired, shorter aging periods, say from about 20 30 minutes or a longer time, and up to about several hours can be resorted to. Thereafter, the porous SiO coated TiO pigment is recovered from the slurry by filtration. it is then calcined at temperatures above 300 and to 1000 C., and preferably between about 400 600 C. At least 15 minutes of calcination is undertaken at high temperatures of 550 C. with up to 30 minutes of calcination being resorted to with lower, above 300 to 400 C. temperatures. Following calcination, the pigment is ground or otherwise conventionally iinishcd to obtain the final pigment. Freferably, such grinding treatment is carried out in a micronizer or like tluid energy mill, using a steam propellant.

To a clearer understanding of. the invention the following more specific example is given wherein the parts mentioned are by weight. This example is merely illus trative of and is not to be construed as limiting the underlying prineiples and scope of the invention.

L E l.

Four 6000-gram portions of a co-oxidized TiO -Al O pigment containing 1.6% Al O were prepared by following the procedures disclosed in 2,559,638. Each of the portions thus prepared was separately stirred into i2 liters of cold de-ionized water to form a 33% pigmentwater slurry having an initial acidic p in the range of 2-5. The slurry mixtures were then heated to 60 C. and stirred with a standard propeller mixer for 30 minutes while being maintained at the temperature men tioned. A solution containing 200 grains of SiO /liter as sodium silicate was then added to the four pigment slurries thus separately prepared to obtain four pigment mixtures containing 2%, 5%, 10% and l5% by weight of SiO The pH of these slurries ranged from 8il. Each pigment mixture was then held at 60 C. for a period of 60 minutes with accompanying mild agitation. and the pi t of each slurry was then lowered to 5.56.5 through the addition of sutTicient sulfuric acid. The acidified slurries were then filtered and the pigment products were recovered, then washed and were then variously calcined for 30 minutes shown in Table I below. The calcined pigments were then ground separately in a fluid energy mill to provide the desired fine-textured products and were separately incorporated in a standard melamine formaldehyde plastic laminate and tested for non-discoloration ir standard test applied to pigment candidates intended for use in laminated apcrs prepared under pressure using conventional type resins, with the following results:

TABLE I Discoloration Pigment Percent Calcination in pa a Sample nit; teinp., (J. laminates" 2 None 4 .2 550 :s 2 450 T 5 None 5 5 5; ll 5 450 ti None l 0 450 .l None l 450 t) 5 450 U 7 5 Noun 4 T 5 400 7 7 5 5t 8 T 000 is T 70!) b- 7 800 l\ 7. 000 7% lll'lllilltlt by coating a piece or white blotter pup Llltlzllillllt lorinultlchytle resin solution containing, 5th,, lllttl drawing this rosin down with a. doctor blade to lorin it llllll 0.010 thick, The coated paper is placed between two melamine formaldehyde lilins and heated at: 205 R lllltill' ltttlt) p g. pressure until bonded, The laniin; c is placed in a l ttt-UllltEll l'or 2 L hours to simulate weather lions. lpon visual comparison with the unwonthcretl saut- IllU, which is given it value of 10 for no yellowing on 2L 'tle whore t) is the worst yellowing, the above values were tlt"l.tl'llllllttl.

Although described as applied to particular embodimerits, the invention is not, as already noted, limited. thereto. Jt ater-soluble alkali metal sodium and potassium ilicates are particularly useful, with sodium silicate, containing a SiO :h-la O ratio of about 3.8:1 by Weight, besing especially preferred. ln general, however, use is contemplated of the various water-soluble silicates, espe cially alkali metal silicates, which form soluble acid salts which can be washed out of the pigment, as well as mixtures of these silicates. After silicate solution addition to the acidic, mechanically agitated slurry suspension, the pr-I of the suspension is moderately basic and ranges from pH 9J1. The pigment can be aged in the tank in this basic solution for an hour or so prior to neutralization by mineral or organic (acetic acid) addition. After the pH has been readjusted to 66.5, it is further aged for at least minutes prior to filtration and drying. if desired, acidification of the TiO suspension to a pH of 1-1.5 or lower can be resorted to prior to the addition of the silicate solution. Again, in the pigment drying operation the temperatures employed are maintained below 200 C. and preferably are within the range of from about 1Z0-l40 C.

The temperature and conditions of treatment under which SiO coating is ei'lected will be found to affect the porosity of tie silica coating appliec to the pigment. At relatively higher temperatures (70 Cl00 C.) a more dense type of coating forms on the pigment, while with the use of lower temperatures (40 C.-70 C.), the pre icrred porous form of coating will result. A porous coating permits penetration by acid into the substrate or TiG A1 6 base, and a coated pigment is characterized by the ease with which Tic is leached therefrom. TiO -AI O co-o1tidized pigments with a 225% silica treatment con tain from 0.1% to 0.3% soluble TiO and from 0.4% to 0.6: a soluble M 0 when treated with 15% sulfuric d and from 0.3% to 0.8% soluble TiO and 0.25%

soluble Al 0 with Co ng a rutile TiO -Al O p g sole tree .ing agent and calcining in accordance with the invention will be found to provide a superior pigment product over a straight TiOg substrate treated through ecipitation with an alumina'silicate coating and obviates ity of applying a plurality of treating agents such as TiO and Al G in tldition to Advantageously, it will be found to suitably combine with all.

intent with silica as the commonly used paper laminating plastics to produce pigmented resinous materials and particularly an opacified white laminated paper which desirably resists discoloration and yellowing when exposed to the atmosphere and to ultraviolet light.

I claim as my invention:

1. As a new pigment composition, calcined coated TiO pigment containing as an ingredient from 0.1 to 10% by weight A1 based on the TiO content of the said pigment and formed by the co-oxidation of TiCl ALCl having a porous coating consisting essentially of from l25% by weight of SiO based on the TiO content of said pigment.

2. The product of claim 1 in which the porous SiO coating is present in from 2-5% by weight.

3. The product of claim 1 containing from .1-10% A1 0 and from 1-25% of porous SiO 4. The product of claim 1 containing from .5 to 3.5% A1 0 and from 2-5% of porous SiO 5. A process for producing a porous coated pigment of Ti0 containing from 0.1 to 10% by weight A1 0 based on the TiO content of the said pigment and formed by the co-oxidation of TiCl -AlCl comprising forming a hot 40-70" C. acidic, aqueous slurry suspension containing 20-40% by weight of said pigment, incorporating with accompanying agitation a water-soluble silicate solution therein until the amount of SiO present ranges from 125%, based on the TiO present, aging the resulting mixture at a pH of at least 9 and thereafter adjusting said pH to not to exceed 6.5, thence aging of the acidified slurry for from 20 to 60 minutes, recovering the resulting pigment coated with porous SiO calcining the product at a temperature above 300 C. and to as high as 1000 C., and recovering the resulting calcined SiO coated pigment product.

6. The process of claim 5 in which incorporation of the alkali metal silicate solution is continued until the amount of SiO present ranges from 25%, adjustment of the pH to a range of 6-6.5 is undertaken and the recovered porous SiO coated product is calcined at from 400600 C.

7. The process of claim 6 in which the alkali metal silicate is sodium silicate.

8. The process of claim 7 in which the amount of sodium silicate solution used contains from -300 grams/ liter SiO the aging treatment is carried out under a pH of from 9 to 11 for a period of about 30 minutes, adjustment of the pH of the mixture to from 6-6.5 is brought about by mineral acid addition, and the neutralized slurry is further aged for a period of about 30 minutes.

References Cited UNITED STATES PATENTS 2,296,636 9/1942 Hanahan 106-300 2,671,031 3/1954 Whatiely 106300 2,780,558 2/1957 Wilcox 106300 2,885,366 5/1959 Iler 106-300 3,035,966 5/1962 Siuta 106300 3,146,119 8/1964 Ritter l06-3OO 3,251,705 5/1966 Rieck et al. 106300 3,316,204 4/1967 Lederer 106-300 TOBIAS E. LEVOW, Primary Examiner H. M. S. SNEED, Assistant Examiner US. Cl. X.R. 

